MXPA98007543A - Non-aromatic polygenic acid to improve insectic absorption - Google Patents

Abstract

The present invention relates to: An insecticide composition is improved from the point of view of its ability to be absorbed by insects, such as the red ant, particularly dithiophosphate ester pesticides by the addition of a small amount of a non-aromatic polyorganic acid soluble in water or a salt form thereof such as polyaspartic acid, particularly preferred with a molecular weight within a scale of about 3000 to 40.0

Description

NON AROMATIC PQLIORGANIC ACID TO IMPROVE INSECTICIDE ABSORPTION BACKGROUND OF THE INVENTION This invention relates to insecticides. Particularly, in a preferred aspect, it relates to an improved method for increasing the effectiveness of the insecticides of the ofosphates in absorption by certain insects to effect the annihilation. The dithiophosphate insecticides of the type to which the present invention refers can be represented by the formula R, 0 S \ || P-S-CHCOOR3 / (R20 CHjgCOOR. wherein Rt, R2, R3 and ^ is each a hydrocarbon radical attic or aromatic. Such esters are well known and can be conventionally prepared, for example, by reacting a 0-d-alkyldiophosphate with a dialkyl maleate as described in accordance with the US patent. No. 2,578,652. A well-known and typical ester of this class is 0.0-dimet? l-S- (1, 2-dicarboethoxy et? 1) d thiophosphate which is commercially available as "Malath?" on R. It is with this latter compound that the test experience with the present invention. The following description applies to dithiophosphate ester insecticides in general, and as explained below, of a wider class of insecticides as well. Thus, it is to be understood that the process herein is equally applicable to other insecticides in addition to the di thiophosphate esters. As mentioned hitherto, such dithiophosphate ester insecticides are known and have been known and effective for many years. However, its effectiveness against some insects of which the red-red ant is only an example, has been limited to a certain degree at lower concentrations. Other classes of classical insecticides in addition to organophosphates and d-thiophosphate esters in particular also need to improve their effectiveness for certain insects. Examples of these other classes of insecticides include carbamates, chlorinated hydrocarbons, synthetic pyrethroids, growth regulators in insects, or botanicals such as nicotine plant derivatives and natural insecticides such as boron and arsenic compounds. These are all within the scope of the present invention. Furthermore, in order to minimize the risks of contamination, there are always ongoing efforts to increase the effectiveness of known insecticides from the point of view of the ability to achieve the same level of effectiveness, but with less insecticide. Accordingly, a main objective of the present invention is to provide a composition that improves the effectiveness of certain classical types of insecticides, particularly the preferred pesticide of dithiophosphate as the Malathion. "Another objective of the present invention is to achieve an improvement in the effectiveness of insecticides by improving the ability of insecticides to be absorbed by the cell membranes of the outer layers of insect cells, thus substantially increasing the effectiveness and thus allowing the reduction of the treatment and the dose level required Another objective of the present invention is to provide an insecticide effectiveness by improving the composition which uses as an additive one that is free from contamination that is environmentally unobjectionable. The method and means for achieving each of the aforementioned objects will be apparent from the detailed description of the invention given below.

BRIEF DESCRIPTION OF THE INVENTION The insecticidal composition which comprises an insecticide such as the pesticide dithiophosphate ester, particularly Malathion®, in a combination of the preferred composition with an effective amount that improves the absorption of water-soluble non-aromatic polyorganic acid or a salt form of said acid, particularly polyaspartic acid. In a broader aspect, the invention also involves a method for improving the effectiveness of the dosage of certain classes of insecticide by adding to them an auxiliary for the effectiveness of penetration through the membrane, such as the acid pol. ico DETAILED DESCRIPTION OF THE INVENTION The present invention has a premise on the fact that it has been discovered that certain compounds, called certain polymeric organic amino acids, as stated in the above patent of E.U.A. 5,350,735, commonly owned, which, together with each of the continuation requests in part, is called serial No. 08 / 313,436, filed on September 27, 1994, serial No. 08 / 439,279, filed on November 11, 1994. May 1995, and Serial No. 08 / 447,784, filed on May 23, 1995, all those descriptions being thus incorporated by reference, can be effectively used in the improvement of the penetration of the dithiophosphate ester insecticides such as MalathionB through the cells of the outer surface of an insect, such as red ants.

The invention, of course, is not limited to the treatment of red ants, but can be effectively used to treat any of the insect pests for any agricultural or horticultural crop, including fruits, cereals, vegetables, flowers and ornamentals. The invention is also useful for any application where the insecticides are used to control insect pests, such as in houses, farm buildings, grain elevators, greenhouses or insect pest control in a general environment, -bars like ants, cockroaches, spiders »fleas, house flies and the like, as well as carriers of diseases and insects that cause discomfort such as mosquitoes, chiggers, black flies, horse flies and the like. In general, the polymeric organic acid can simply be added to the liquid from the insecticide, generally within a weight ratio of 1: 100 (polyaspartate: insecticide) to 100: 1 (polyaspartate: insecticide). Polymeric organic acids, to be suitable for the practice of the present invention, must be water-soluble, non-aromatic and must have a molecular weight sufficiently large to prevent absorption into the plant system. To that end, units of non-aromatic polymeric organic acid (residues) or groupers, in the linear polymer chain that constitutes the acids Organic acidic polymers having a molecular weight in excess of about 100,000 commonly show little solubility in water for the purposes of the present. Thus "for the purposes of the present", a polymeric organic acid of molecular weight no greater than about 100,000 is preferred. Particularly the preferred molecular weight is on a scale of about 1,500 to about 100,000. Illustrative are polymeric organic acids, with or without carboxylic acid, thiocarboxyl acid, and / or amino side chains such as, for example, polyacrylic acid, poly-itartaric acid, poly-alialic acid, polylysine, acid glutamic acid, polyaspartic acid, polyethylene glycol, polyclistein, polysisteine / glutamic acid, mixtures of the foregoing or their salts, copolymers of the foregoing, and the like. Therefore, random or block copolymers or terpolymers of various organic acids are also within the scope of the present invention as the insecticide of the polymeric acid thereof. For example, the constituent of the polymeric acid used may be a block copolymer of aspartic acid residues and residues of L-lactic acid »a random copolymer of aspartic acid residue and glycolic acid residues» a conjugated protein constituted by residues of amino acid residues interconnected by one or more residues of pol carboxylic acid »a copolymer of acrylic acid and acrylamide» and similar. Polymers of organic acids are commercially available. Moreover, such polymeric acids, especially poly (amino acids), can be made, inter alia, by thermal condensation methods. See, for example, the patent of E.U.A. No. 5,057,597 to Koskan, Little et al., American Chemical Society 97: 263-279 (1991), and the patent of E.U.A. No. 4,696,981, Harada et al. Although the foregoing description has been presented with the particular examples of the classical organophostolate esters such as Malathion F '"other insecticides (as already mentioned above) can be used with the same improved effectiveness observed. For example, in the specific working examples given below, data are presented for carbamates such as 1-naft I and Icarbamate and also for Diazinon®. The insecticide, in combination with polyorganic acid or polyorganic salt, such as pol-aspartic acid, can be applied through direct spray, powder, or by flood "can be applied in granulated form" as well as "wet powder" in spray »as a lure» as attractive »or it can be applied volleyball. In summary »the method of application is not critical. The following examples are offered for an additional illustration "but do not necessarily limit the procedure and to demonstrate the composition of this invention as shown to improve the effectiveness of the insecticide compared to insecticides alone. It will be apparent to those skilled in the art that certain modifications to the methods and components can be made without departing from the spirit and scope of the invention described herein.

EXAMPLE 1 A series of experiments were conducted with Malathion® "which is a dithiophosphate ester insecticide with a formula as described above" where Rx and R ^ are met "and R"? and R ^ are ethyl. Chemically named 0 »0« - (di eti 1) -S- (1 »2 dicarboethoxyeti 1) -di thio osphate. The tests were used to control the imported red ants. By way of background, "the imported red ant has migrated to the entire southern United States and is predicted to continue moving to areas with similar ecological conditions" such as Denver »Colorado. The mounds of imported red ants are a nuisance in the gardens of houses "in industrial areas" in farmland agriculture and grazing land. The imported red ant attacks humans' pets and wildlife. The bites or "stings" recently come to be infected and have caused blindness in animals and extensive discomfort in humans for periods of two weeks or more. Is therefore desirable to control these ants. In all previous experiments »polyaspartic acid refers to 41% (by weight) of the sodium polyaspartate solution» having a molecular weight between 3,000 and 5,000 »in water. The insecticide solutions were prepared »solution 1 contained one tablespoon for every 3.78 1 (2 quarts / 3.78 1) of Malathion® in water. Solution 2 contained 2 tablespoons / 3.78 1 of Malathion® and 2 tablespoons / 3.78 1 of polyaspartic acid. The two solutions were applied in active mounds of red ants at ambient temperatures between 26.6 ° and 29.4 ° C. The purpose of this test was to evaluate a moderately mild insecticide alone and with polyaspartic acid with membrane enhancement aids added to Malathion®. Ten mounds of active red ants were sprayed at room temperature from 26.6 ° C to 29.4 ° C. This was treated with Malathion® alone and with Malathion® plus the pol-aspartic acid described above. Observations were made 4 hours after treatment and 24 hours after treatment for the activity of each mound. A plastic spoon was inserted into each mound and extracted several times in rapid succession to aggravate the ants. The internal activity of the mounds was evaluated by digging inside each mound with a sharp peak shovel to observe the activity and configuration of the channel. The results are shown in the following table, Percentage of Controlled Ants Imported red treatments 24 hours 4 hours MALATHION * O MALATHIONR + 99 * lOO Polyaspartic acid PM 300-500 * Only one ant observed; possibly an explorer From the above table it can be seen that polyaspratic acid, when added to Malathion, "effectively controls the imported red fire ants, while Malathion" by itself virtually does not provide control. When the former was repeated with other insects such as spiders, mites, other ants and bees, similar results were obtained in the effectiveness of annihilation at the same dosage level and this was dramatically improved.

EXAMPLE 2-6 The marked averages of insecticides used in the following examples are as follows: MalathionR-2 small spoons per 3.78 i; DiazinónR-2 small spoons by 3.78 1, "Sevín" -1 tablespoon by 3.78 1. The insecticide solutions »with or without the added polyaspartic acid» were prepared. The treatment of insects was supplemented as follows: before the introduction of the insects »50 ml of insecticide solution was added to each of the several bottles of a quarter. The bottles were sealed, shaken »emptied and allowed to dry for two hours in a room at room temperature. The imported fire ants (HRFI) were treated with insecticide carbamate (1-Naphthyl methyl 1 carbamate), D azinon (0,0-diethyl l-0-C6-methyl-2- (l-meti leti 1) -4-p rimidi-ni 1 Ufosforot? Oate) and Malathion® and in combination with polyaspartates. The ants were placed and sealed in containers "and their mortality and nonscience rates were taken over time. Table 1 shows that there were few differences in HRFI mortality with a recorded 0.03 rate of Sevín® (1-naphthylmethylcarbamate) used in combination with IX (1 tablespoon / 3.78 1) or 2X (2 tablespoons / 3.78 1 ) of aspartates. The percentage of unconsciousness (table 2), however, "increased significantly from one to two hours of exposure with 2X polyaspartates in combination with the 0.03 marked SevínR rate. Malathion® (0.3 marked rate) »in combination with IX and 2X poliaspartate rates signifi- cantly increased mortality of HRFIs in one hour as shown in Table 3. Table 4 shows the significant effects of the polysaccharides in combination with a marked rate of 0.25 of DiazinónR applied throughout one hour of exposure. At marked O.125 rates in Diazinón, the combination of aspartates was significantly more effective over the mortality of the HRFI (Table 5) at 2 hours. At a 4-hour exposure the Diazinon® at a rate marked at 0.03 shows a significant increase in the mortality of the HRFI with an IX and 2X polyaspartate rates compared with the insecticides only (Table 6).

TABLE 1 SEVIN AT 0.03 marked rate Hours Active% Mortality 2 insecticide only 26.1% 2 insecticide »IX 27.1% 2 insecticide» 2X 35.1% TABLE 2 SevínR a 0.Q3 marked rate Hours Active% Inconsc ency 1 insecticide only 18.7% 1 insecticide »IX 13.6% 1 insecticide» 2X 80.7% 2 insecticide only 80.0% 2 insecticide »IX 80.0% 2 insecticide» 2X 94.0% TABLE 3 Malathion® at 0.03 marked rate Active Hours% Mortality 1 insecticide only 47.7% 1 insecticide »IX 79.3% 1 insecticide» 2X 76.0% TABLE 4 Diazi non "at 0.25 marked rate Active Hours% Mortality 1 insecticide only 70.8% 1 insecticide »2X 91.0% TABLE 5 D? Az ónR to 0.125 marked rate Hours ACTIVO% Mortality 2 insecticide only 53.4% 2 insecticide »2X 6 .9% TABLE 6 Diazi ónw at 0.03 marked rate Hours Active% Mortality 4 insecticide only 10.7% 4 insecticide »IX 68.5% 4 nsecticide» 2X 91.8% It can be seen from this that the invention completes at least all of its established objectives.

Claims (15)

NOVELTY OF THE INVENTION CLAIMS

1. - An insecticide composition comprising an insecticide and a small but effective amount of insecticide absorption enhancement of at least one non-aromatic polyorganic acid »soluble in water or a salt thereof which is a poly-amino acid» an amino acid copolymer or a derivative of polyols and copolymers.

2. An insecticide composition comprising an insecticide and a small but effective amount of insecticide absorption enhancement of a non-aromatic polyorganic acid "soluble in water or a salt thereof which is a poly-amino acid" or a copolymer of said acid »Selected from the group consisting of polyaspartic acid» pollutamic acid. pol igl icina »polylysine. a copolymer of cysteine and glutamic acid and a terpolymer of cysteine »glutamic acid» and aspartic acid »pol amino acid having a molecular weight greater than 1500.

3.- The insecticide composition in accordance with re-indication 1» characterized further because the insecticide is selected from the group consists of organo-osphates, carbamates, chlorinated hydrocarbons »pyreteroids, and botanical and natural compounds of boron and arsenic.

4.- The composition of the insecticide in accordance with

re vindication 2 »further characterized in that the insecticide is a dithiophosphate of the formula:

wherein x »R2» R3 and R ^ are each an aliphatic or aromatic radical.

5. The composition of insecticide according to the rei indication 3 »further characterized because R ^, R2, R3 and R ^, are alkyls of C ^ to Cs. & .- The composition of the insecticide in accordance with the rei indication 4 »further characterized R ^. and R_, they are methyl and

Ra and R- »sor? eti 1.

7. The insecticide composition according to claim 4 »further characterized in that the pol amino acid is polyaspartic acid.

8. The insecticide composition according to claim 2 »further characterized in that the polyaspartic acid has a molecular weight on a scale of about 1500 to about 100,000.

9. The insecticide composition according to claim 8 »further characterized in that the polyacid is pol-aspartic acid having a molecular weight on a scale of about 3000 to 40,000.

10. - The insecticide composition according to claim 1, further characterized in that the amount in the form of non-aromatic polyorganic salts or acids is therefore a weight ratio of about 1: 100 of polyaspartate: di tio os ato to about 100: 1 of pol aspartate: di thiophosphate.

11. The insecticide composition according to claim 1, further characterized in that the amount in the form of non-aromatic polyorganic salts or acids are therefore about 1: 100 of polyaspartate to dithiophosphate at about 20: 1 of polyaspartate to dithio osphate.

12. The insecticide composition according to claim 2 »further characterized in that the organo-osphate which is OO-dimet 1-S- (1» 2-dicarboethoxyethyl) -dithiophosphate and the forms of acids or polyorganic salts are thus polyaspartic acids having a molecular weight from 3000 to 40,000.

13. The insecticide composition according to claim 2 »further characterized in that the phosphate organ is 0.0-diethyl 0-C6-methyl 1-2- < 1-met leti 1) -4-pyrimidini-11 phosphorothioate and acid forms or organic pol salts are therefore polyaspartic acids having a molecular weight from 3000 to 40 ° C.

14. The insecticide composition according to claim 2, further characterized in that the insecticide is a carbamate and the acid form or polyorganic salt at the same time.

a

both is a polyaspartic acid having a molecular weight from 3,000 to 40,000.

15. A method to improve the effectiveness of insecticide absorption, the method comprising: adding to the insecticide a small but effective amount of improvement of insecticide absorption of a water-soluble non-aromatic polyorganic acid or a salt form thereof. which is a poly-amino acid or a copolymer acid selected from the group consisting of pol-aspartic acid »pollutamic acid, pol igline, »polylysine» a copolymer of cysteine and glutamic acid and a terpolymer of cysteine »glutamic acid and aspartic acid, polyamino acid having a molecular weight greater than 1500. 16.- The method of conformance with the reference 15 , further characterized in that the poly-amino acid is pol-aspartic acid. 17. The method according to claim 15, further characterized in that the polyaspartic acid has a molecular weight within a scale of about 1500 to about 100,000. 18. The method according to claim 15 »further characterized in that the polyamino acid is pol-aspartic acid co having a molecular weight of a scale of about 3000 to 40,000. 19.- The method according to the claim

15 »characterized in addition because the quantity of the forms of

salts or non-aromatic organic pol acids are therefore from a weight ratio of about 1: 100 of polyapartate: d-thiophosphate to about 10: 1 of polyaspartate: d-thiophos ato. 20.- The method according to the claim

15"further characterized in that the amount of the non-aromatic polyorganic acid or salt forms is from about 1: 100 polyaspartate: dithiophosphate to about 20: 1 polyaspartate: di thiophosphate, 21.- The method according to rei indication

15"further characterized in that the dithiophosphate in 0.0-dimethyl-S- (1'-dicarboethoxyethyl) di thiophosphate and the salt form or organic pol acid is polyaspartic acid having a molecular weight from 3000 to 40,000. 22. The method of compliance with the rei indication

15"further characterized in that the phosphate organ is 0.0-diethyl O-C6-methyl 1-2- (1- eti leti 1) -4-pyrimid? Ni or 11 in the form of organic pol salts or acids and the phosphorothioate is a polyaspartic acid having a molecular weight from 3000 to 40,000. 23. The method according to the indication 15 »further characterized in that the insecticide is a carbamate and is 1-naphthyl-meth-1-carbamate and the forms of salts or pol-organic acids are therefore polyaspartic acid having a molecular weight from 3000 to 40,000. 24.- The method according to the indication 15 »characterized in that the pesticide is a pesticide

dithiophosphate. 25.- The method according to the rei indication 24 »further characterized because the pesticide is a dithiophosphate ester of the formula:

and Rx, R2, R3 and R ^ are al C to Ca. 26.- The method according to claim 24, wherein Ra, R_, R3 and ^ are each selected from the group consisting of C ^. and C2. 27.- The method according to the indication 24, further characterized in that the pesticide dithiophosphate is 0.0- dimet l-S- (1,2-dicarboxyethoxyeti-1) -diio osphate. 28.- The method according to claim 15, also characterized because the insecticide is a carbamate insecticide.